DE19955861A1 - Continuous production of crosslinked gel polymer for use e.g. as an absorber involves polymerisation of monomers in a multi-screw machine with heat removal by evaporation of water and product take-off - Google Patents
Continuous production of crosslinked gel polymer for use e.g. as an absorber involves polymerisation of monomers in a multi-screw machine with heat removal by evaporation of water and product take-offInfo
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- DE19955861A1 DE19955861A1 DE19955861A DE19955861A DE19955861A1 DE 19955861 A1 DE19955861 A1 DE 19955861A1 DE 19955861 A DE19955861 A DE 19955861A DE 19955861 A DE19955861 A DE 19955861A DE 19955861 A1 DE19955861 A1 DE 19955861A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J14/00—Chemical processes in general for reacting liquids with liquids; Apparatus specially adapted therefor
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/20—Stationary reactors having moving elements inside in the form of helices, e.g. screw reactors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- B01J2219/00027—Process aspects
- B01J2219/00033—Continuous processes
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00054—Controlling or regulating the heat exchange system
- B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
- B01J2219/00058—Temperature measurement
- B01J2219/00063—Temperature measurement of the reactants
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
- B01J2219/00085—Plates; Jackets; Cylinders
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00094—Jackets
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00121—Controlling the temperature by direct heating or cooling
- B01J2219/00123—Controlling the temperature by direct heating or cooling adding a temperature modifying medium to the reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00121—Controlling the temperature by direct heating or cooling
- B01J2219/00128—Controlling the temperature by direct heating or cooling by evaporation of reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00162—Controlling or regulating processes controlling the pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00164—Controlling or regulating processes controlling the flow
- B01J2219/00166—Controlling or regulating processes controlling the flow controlling the residence time inside the reactor vessel
Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur kontinuier lichen Herstellung von vernetzten feinteiligen gelförmigen Poly merisaten.The present invention relates to a method for continuous Lichen production of cross-linked fine gel-like poly merisates.
Aus der DE-OS 34 32 690 ist ein Verfahren zur kontinuierlichen Herstellung von vernetzten Polymerisaten bekannt, bei dem man wasserlösliche Monomere in Gegenwart eines Vernetzers und von In itiatoren in einem Kessel polymerisiert, der mit einer Mehrzahl von parallel zueinander angeordneten rotierenden Rührerwellen ausgerüstet ist, die mit Rührerblättern versehen sind. Die Polymerisation wird kontinuierlich in einem Zweiarm-Typkneter oder beispielsweise in einem Dreischaftkneter durchgeführt. Bei diesem Reaktortyp findet eine starke Rückvermischung statt, so daß die Monomerlösung auf das fein zerteilte wasserhaltige Gel polymere gegeben wird und die Polymerisation des Monomeren auf der Oberfläche des Polymergels abläuft. Die so herstellbaren feinteiligen Polymerisatgele haben einen relativ hohen Rest monomergehalt.DE-OS 34 32 690 describes a process for continuous Production of crosslinked polymers known, in which one water-soluble monomers in the presence of a crosslinker and of In itiators polymerized in a boiler with a plurality of rotating stirrer shafts arranged parallel to each other is equipped with stirrer blades. The Polymerization is carried out continuously in a two-arm type kneader or carried out, for example, in a three-shaft kneader. At this type of reactor is strongly mixed back, so that the monomer solution on the finely divided water-containing gel polymer is given and the polymerization of the monomer runs off the surface of the polymer gel. The so producible finely divided polymer gels have a relatively high residue monomer content.
Die EP-A-223 063 lehrt ein Verfahren zur kontinuierlichen Her stellung von vernetzten feinteiligen gelförmigen Polymerisaten in einem einwelligen zylindrischen Mischer, dessen Mischsegmente eine Förderung der Stoffe vom Anfang zum Ende des zylindrischen Mischers bewirken. Die Polymerisation wird bei einem Druck von 100 bis 800 mbar durchgeführt, was einen hohen apparativen Auf wand bedeutet, um den Druck zu regulieren. Die Monomere müssen über ein Druckhalteventil in den Reaktor dosiert werden, welches leicht zupolymerisiert. Darüberhinaus haben beide Verfahren ein unbefriedigend breites Verweilzeitspektrum und einen oszillieren den Produktaustrag.EP-A-223 063 teaches a process for continuous production position of cross-linked, finely divided gel-like polymers in a single-shaft cylindrical mixer, the mixing segments a promotion of fabrics from the beginning to the end of the cylindrical Effect mixer. The polymerization is carried out at a pressure of 100 to 800 mbar carried out, which is a high apparatus wall means to regulate the pressure. The monomers have to be metered into the reactor via a pressure control valve, which slightly polymerized. In addition, both procedures have one unsatisfactorily wide range of dwell times and an oscillate the product discharge.
Daher war es Aufgabe der vorliegenden Erfindung, ein apparativ einfaches Verfahren mit guter Raum/Zeit-Ausbeute zur Verfügung zu stellen, dessen Produkt ein gleichmäßiges Polymergel mit geringem Restmonomergehalt ist.It was therefore an object of the present invention to provide an apparatus simple process with good space / time yield available too ask whose product is a uniform polymer gel with low Residual monomer content.
Demgemäß wurde ein Verfahren zur kontinuierlichen Herstellung von
vernetzten, feinteiligen, gelförmigen Polymerisaten durch Copoly
merisieren von
Accordingly, a process for the continuous production of crosslinked, finely divided, gel-like polymers by copoly merize
- a) wasserlöslichen, monoethylenisch ungesättigten Monomeren,a) water-soluble, monoethylenically unsaturated monomers,
- b) 0,001 bis 5 Mol-% bezogen auf die Monomere (a), mindestens zwei ethylenisch ungesättigte Doppelbindungen enthaltenden Monomeren undb) 0.001 to 5 mol%, based on the monomers (a), at least containing two ethylenically unsaturated double bonds Monomers and
- c) 0 bis 20 Mol-% bezogen auf die Monomere (a) wasserunlöslichen monoethylenisch ungesättigten Monomerenc) 0 to 20 mol% based on the monomers (a) water-insoluble monoethylenically unsaturated monomers
in 20 bis 80 gew.-%iger wäßriger Lösung in Gegenwart von Initia tor bei Temperaturen von 0 bis 140°C, wobei man die wäßrige Lösung der Monomeren zusammen mit dem Initiator und einem Inertgas kontinuierlich einem Mischkneter mit mindestens zwei achsparallel rotierenden Wellen zuführt, wobei sich auf den Wellen mehrere Knet- und Transportelemente befinden, die eine Förderung der am Anfang des Mischkneters zugegebenen Stoffe in axialer Richtung zum Ende des Mischers bewirken, gefunden, bei dem der Anteil der Wärmeabfuhr durch Verdampfung von Wasser aus dem Reaktionsgemisch mindestens 5% der Reaktionswärme und der Anteil der Wärmeabfuhr durch Produktaustrag mindestens 25% dar Reaktionswärme beträgt und die restliche Wärmeabfuhr über Kühlung der Reaktorwände er folgt.in 20 to 80 wt .-% aqueous solution in the presence of Initia tor at temperatures from 0 to 140 ° C, wherein the aqueous solution of the monomers together with the initiator and an inert gas continuously a mixer kneader with at least two axially parallel rotating shafts, with several on the shafts Kneading and transport elements are located, which promote the am Beginning of the mixer kneader added substances in the axial direction effect at the end of the mixer, found in which the proportion of Heat removal by evaporation of water from the reaction mixture at least 5% of the heat of reaction and the proportion of heat dissipation is at least 25% of the heat of reaction due to product discharge and the remaining heat dissipation via cooling the reactor walls follows.
Wasserlösliche monoethylenisch ungesättigte Monomere der Gruppe
(a) sind beispielsweise ethylenisch ungesättigte C3- bis C6-Car
bonsäuren, deren Amide und Ester mit Aminoalkoholen der Formel
Water-soluble monoethylenically unsaturated monomers of group (a) are, for example, ethylenically unsaturated C 3 -C 6 -carboxylic acids, their amides and esters with amino alcohols of the formula
in der R4 C2- bis C5-Alkylen und R1, R2, R3 unabhängig voneinander Wasserstoff, Methyl, Ethyl oder Propyl bedeutet. Bei diesen Verbindungen handelt es sich beispielsweise um Acrylsäure, Meth acrylsäure, Crotonsäure, Itaconsäure, Maleinsäure, Fumarsäure sowie den Alkali- oder Ammoniumsalzen dieser Säuren, Acrylamid, Methacrylamid, Crotonsäureamid, Dimethylaminoethylacrylat, Diethylaminoethylacrylat, Dimethylaminopropylacrylat, Dimethyl aminobutylacrylat, Diethylaminoethylmethacrylat, Dimethylamino ethylmethacrylat, Dimethylaminopropylacrylat, Dimethylaminoneo pentylacrylat und Dimethylaminoneopentylmethacrylat. Die basi schen Acrylate und Methacrylate werden in Form der Salze mit starken Mineralsäuren, Sulfonsäuren oder Carbonsäuren oder in quaternisierter Form eingesetzt. Das Anion X⊖ für die Verbindungen der Formel I ist der Säurerest der Mineralsäuren bzw. der Carbonsäuren oder Methosulfat, Ethosulfat oder Halogenid aus einem Quaternierungsmittel.in which R 4 is C 2 to C 5 alkylene and R 1 , R 2 , R 3 independently of one another are hydrogen, methyl, ethyl or propyl. These compounds are, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid and the alkali metal or ammonium salts of these acids, acrylamide, methacrylamide, crotonic acid amide, dimethylaminoethylacrylate, diethylaminoethylacrylate, dimethylaminopropylacrylate, dimethylaminoethylaminoethylamylamethylamylamethylamethylamylamethylamethylaminoethylamylamethylamethylamylamethylaminoethylamylamethylamethylaminoethylamylamethylaminoethylamylamethylaminoethylaminoamylamethylaminoethylamylaminoethylaminoethylamylamethylaminoethylaminoethylaminoethylamylaminoethylaminoethylaminoethylaminoethylaminoethylaminoethylaminoethylaminoethylaminoamethylaminoethylaminoethylaminoethylaminoethylaminoethylaminoethylaminoethylaminoethylaminoethylaminoethylaminoethylamylate Methylamino Acrylate as well , Dimethylaminoneopentyl acrylate and dimethylaminoneopentyl methacrylate. The basic acrylates and methacrylates are used in the form of the salts with strong mineral acids, sulfonic acids or carboxylic acids or in quaternized form. The anion X ⊖ for the compounds of formula I is the acid residue of the mineral acids or the carboxylic acids or methosulfate, ethosulfate or halide from a quaternizing agent.
Weitere wasserlösliche Monomere der Gruppe (a) sind N-Vinylpyrro lidon, Acrylamidopropansulfonsäure, Vinylphosphonsäure und/oder Alkali- bzw. Ammoniumsalze der Vinylsulfonsäure. Die anderen Säuren können ebenfalls entweder in nicht neutralisierter Form oder in partiell bzw. bis zu 100% neutralisierter Form bei der Polymerisation eingesetzt werden. Als wasserlösliche Monomere der Gruppe (a) eignen sich auch Diallylammoniumverbindungen, wie Di methyldiallylammoniumchlorid, Diethyldiallylammoniumchlorid oder Diallylpiperidiniumbromid, N-Vinylimidazoliumverbindungen, wie Salze oder Quaternisierungsprodukte von N-Vinylimidazol und 1-Vinyl-2-methylimidazol, und N-Vinylimidazoline, wie N-Vinylimi dazolin, 1-Vinyl-2-methylimidazolin, 1-Vinyl-2-ethylimidazolin oder 1-Vinyl-2-n-propylimidazolin, die ebenfalls in quaterni sierter Form oder als Salz bei der Polymerisation eingesetzt wer den.Other water-soluble monomers of group (a) are N-vinyl pyrro lidon, acrylamidopropanesulfonic acid, vinylphosphonic acid and / or Alkali or ammonium salts of vinyl sulfonic acid. The others Acids can also be used in either non-neutralized form or in partially or up to 100% neutralized form at Polymerization can be used. As water-soluble monomers the Group (a) are also suitable diallylammonium compounds, such as Di methyldiallylammonium chloride, diethyldiallylammonium chloride or Diallylpiperidinium bromide, N-vinylimidazolium compounds such as Salts or quaternization products of N-vinylimidazole and 1-vinyl-2-methylimidazole, and N-vinylimidazolines such as N-vinylimi dazolin, 1-vinyl-2-methylimidazoline, 1-vinyl-2-ethylimidazoline or 1-vinyl-2-n-propylimidazoline, also in quaterni form or used as a salt in the polymerization the.
Bevorzugte Monomere der Gruppe (a) sind Acrylsäure, Methacryl säure sowie die Alkali- oder Ammoniumsalze dieser Säuren, Acryl amid und/oder Methacrylamid. Diese Monomere können in jedem be liebigen Verhältnis miteinander copolymerisiert werden.Preferred monomers of group (a) are acrylic acid, methacrylic acid and the alkali or ammonium salts of these acids, acrylic amide and / or methacrylamide. These monomers can be in any any relationship can be copolymerized with each other.
Die Polymerisation der Monomere der Gruppe (a) erfolgt in Gegen wart von Vernetzern (Monomere der Gruppe (b)). Die Vernetzer ent halten mindestens zwei ethylenisch ungesättigte Doppelbindungen. Geeignete Vernetzer sind beispielsweise N,N'-Methylenbisacryl amid, Polyethylenglykoldiacrylate und Polyethylenglykoldimeth acrylate, die sich jeweils von Polyethylenglykolen eines Moleku largewichts von 126 bis 8500, vorzugsweise 400 bis 2000, ableiten, Trimethylolpropantriacrylat, Trimethylolpropantrimeth acrylat, Ethylenglykoldiacrylat, Propylenglykoldiacrylat, Butan dioldiacrylat, Hexandioldiacrylat, Hexandioldimethacrylat, Diacrylate und Dimethacrylate von Blockcopolymerisaten aus Ethylenoxid und Propylenoxid, zweifach bzw. dreifach mit Acryl säure oder Methacrylsäure veresterte mehrwertige Alkohole, wie Glycerin oder Pentaerythrit, Triallylamin, Tetraallylethylen diamin, Divinylbenzol, Diallylphthalat, Polyethylenglykoldivinyl ether von Polyethylenglykolen eines Molekulargewichts von 126 bis 4000, Trimethylolpropandiallylether, Butandioldivinyl ether, Pentaerythrittriallylether und/oder Divinylethylenharn stoff. Vorzugsweise setzt man wasserlösliche Vernetzer ein, z. B. N,N-Methylenbisacrylamid, Polyethylenglykoldiacrylat, Poly ethylenglykoldimethacrylate, Pentaerythrittriallylether und/oder Divinylharnstoff. Die Monomere der Gruppe (b) werden in Mengen von 0,001 bis 5, vorzugsweise 0,005 bis 0,5 Mol-% bezogen auf die Monomere (a) bei der Copolymerisation eingesetzt.The monomers of group (a) are polymerized in counter were from crosslinkers (monomers of group (b)). The crosslinkers ent hold at least two ethylenically unsaturated double bonds. Suitable crosslinkers are, for example, N, N'-methylene bisacrylic amide, polyethylene glycol diacrylates and polyethylene glycol dimeth acrylates, each of polyethylene glycols of a molecule lar weight from 126 to 8500, preferably 400 to 2000, deduce trimethylolpropane triacrylate, trimethylolpropane trimeth acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, butane diol diacrylate, hexanediol diacrylate, hexanediol dimethacrylate, Diacrylates and dimethacrylates from block copolymers Ethylene oxide and propylene oxide, two or three times with acrylic acid or methacrylic acid esterified polyhydric alcohols, such as Glycerin or pentaerythritol, triallylamine, tetraallylethylene diamine, divinylbenzene, diallyl phthalate, polyethylene glycol divinyl ethers of polyethylene glycols with a molecular weight of 126 to 4000, trimethylol propanediallyl ether, butanediol divinyl ether, pentaerythritol triallyl ether and / or divinylethylene urine material. Preferably, water-soluble crosslinking agents are used, e.g. B. N, N-methylene bisacrylamide, polyethylene glycol diacrylate, poly ethylene glycol dimethacrylates, pentaerythritol triallyl ether and / or Divinyl urea. The monomers of group (b) are in quantities from 0.001 to 5, preferably 0.005 to 0.5 mol% based on the Monomers (a) used in the copolymerization.
Die Copolymerisation der Monomere der Gruppen (a) und (b) kann - sofern eine Änderung der Eigenschaften der Copolymerisate ge wünscht wird - zusätzlich noch in Gegenwart von Monomeren der Gruppe (c) durchgeführt werden. Als Monomere der Gruppe (c) kom men beispielsweise Hydroxyethylacrylat, Hydroxypropylacrylat, Hydroxyethylmethacrylat, Hydroxypropylmethacrylat, Acrylnitril und/oder Methacrylnitril in Betracht. Außerdem eignen sich Ester der Acrylsäure oder Methacrylsäure mit 1 bis 18 Kohlenstoffatome enthaltenden einwertigen Alkoholen, z. B. Methylacrylat, Ethyl acrylat, Propylacrylat, Isopropylacrylat, n-Butylacrylat, Iso butylacrylat, Hexylacrylat, 2-Ethylhexylacrylat, Stearylacrylat, die entsprechenden Ester der Methacrylsäure, Fumarsäurediethyl ester, Maleinsäurediethylester, Maleinsäuredimethylester, Malein säuredibutylester, Vinylacetat und Vinylpropionat. Sofern die Monomere der Gruppe (c) zur Modifizierung der wasserlöslichen Polymerisate verwendet werden, setzt man 0,5 bis 20, vorzugsweise 2 bis 10 Mol-% bezogen auf die Monomere (a) ein.The copolymerization of the monomers of groups (a) and (b) can - if a change in the properties of the copolymers ge is desired - additionally in the presence of monomers Group (c) are carried out. Comonomers as group (c) monomers For example, hydroxyethyl acrylate, hydroxypropyl acrylate, Hydroxyethyl methacrylate, hydroxypropyl methacrylate, acrylonitrile and / or methacrylonitrile. Esters are also suitable acrylic acid or methacrylic acid with 1 to 18 carbon atoms containing monohydric alcohols, e.g. B. methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, iso butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, the corresponding esters of methacrylic acid, fumaric acid diethyl esters, diethyl maleate, dimethyl maleate, malein acid dibutyl ester, vinyl acetate and vinyl propionate. If the Monomers of group (c) to modify the water-soluble Polymers are used, 0.5 to 20, preferably 2 to 10 mol% based on the monomers (a).
Die wasserunlöslichen Monomere können, falls sie bei der Copoly merisation miteingesetzt werden, mit Hilfe von Emulgatoren in der wäßrigen Lösung fein verteilt werden. Geeignete Emulgatoren sind beispielsweise ethoxylierte Nonylphenole, ethoxyliertes Ricinusöl, Alkylsulfate, Sorbitanfettsäureester, ethoxylierte Sorbite, ethoxylierte Sorbitanfettsäureester und Alkylsulfonate. Die Emulgatoren werden in einer Menge von 0 bis 3 Gew.-% bezogen auf die Monomere (a) eingesetzt.The water-insoluble monomers, if they are copoly be used with the help of emulsifiers in the aqueous solution can be finely divided. Suitable emulsifiers are for example ethoxylated nonylphenols, ethoxylated Castor oil, alkyl sulfates, sorbitan fatty acid esters, ethoxylated Sorbites, ethoxylated sorbitan fatty acid esters and alkyl sulfonates. The emulsifiers are obtained in an amount of 0 to 3% by weight used on the monomers (a).
Die Polymerisation kann gegebenenfalls in Gegenwart der üblichen Polymerisationsregler erfolgen. Geeignete Polymerisationsregler sind beispielsweise Thioverbindungen, wie Thioglykolsäure, Mer captoalkohole, z. B. 2-Mercaptoethanol, Mercaptopropanol und Mercaptobutanol, Dodecylmercaptan, Ameisensäure, Ammoniak und Amine, z. B. Ethanolamin, Diethanolamin, Triethanolamin, Triethyl amin, Morpholin und Piperidin.The polymerization can optionally in the presence of the usual Polymerization regulators take place. Suitable polymerization regulators are, for example, thio compounds, such as thioglycolic acid, Mer capto alcohols, e.g. B. 2-mercaptoethanol, mercaptopropanol and Mercaptobutanol, dodecyl mercaptan, formic acid, ammonia and Amines, e.g. B. ethanolamine, diethanolamine, triethanolamine, triethyl amine, morpholine and piperidine.
Die Monomere (a), (b) und gegebenenfalls (c) werden in 20 bis 80, vorzugsweise 20 bis 50, insbesondere 30 bis 45 gew.-%iger wäßri ger Lösung in Gegenwart von Polymerisationsinitiatoren miteinan der copolymerisiert. Als Polymerisationsinitiatoren können sämt liche unter den Polymerisationsbedingungen in Radikale zerfal lende Verbindungen eingesetzt werden, z. B. Peroxide, Hydroper oxide, Wasserstoffperoxid, Persulfate, Azoverbindungen und die sogenannten Redoxkatalysatoren. Bevorzugt ist der Einsatz von wasserlöslichen Katalysatoren. In manchen Fällen ist es vorteil haft, Mischungen verschiedener Polymerisationsinitiatoren zu ver wenden, z. B. Mischungen aus Wasserstoffperoxid und Natrium- oder Kaliumperoxodisulfat. Mischungen aus Wasserstoffperoxid und Natriumperoxodisulfat können in jedem beliebigen Verhältnis verwendet werden. Geeignete organische Peroxide sind beispiels weise Acetylacetonperoxid, Methylethylketonperoxid, tert.-Butyl hydroperoxid, Cumolhydroperoxid, tert.-Amylperpivalat, tert.-Bu tylperpivalat, tert.-Butylperneohexanoat, tert.-Butylperisobuty rat, tert.-Butylper-2-ethylhexanoat, tert.-Butylperisononanoat, tert.-Butylpermaleat, tert.-Butylperbenzoat, tert.-Butyl per-3,5,5-tri-methylhexanoat und tert.-Amylperneodekanoat. Wei tere geeignete Polymerisationsinitiatoren sind Azostarter, z. B. 2,2'-Azobis-(2-amidinopropan)dihydrochlorid, 2,2'-Azobis-(N,N-di methylen)isobutyramidin-dihydrochlorid, 2-(Carbamoylazo)iso butyronitril und 4,4'-Azobis-(4-cyanovaleriansäure). Die genann ten Polymerisationsinitiatoren werden in üblichen Mengen einge setzt, z. B. in Mengen von 0,01 bis 5, vorzugsweise 0,1 bis 2 Mol%, bezogen auf die zu polymerisierenden Monomere.Monomers (a), (b) and optionally (c) are in 20 to 80, preferably 20 to 50, in particular 30 to 45 wt .-% aqueous ger solution together in the presence of polymerization initiators which copolymerizes. All of them can be used as polymerization initiators decompose into radicals under the polymerization conditions lend connections are used, for. B. peroxides, hydroper oxides, hydrogen peroxide, persulfates, azo compounds and the so-called redox catalysts. The use of is preferred water-soluble catalysts. In some cases it is an advantage liable to ver mixtures of different polymerization initiators turn, e.g. B. mixtures of hydrogen peroxide and sodium or Potassium peroxodisulfate. Mixtures of hydrogen peroxide and Sodium peroxodisulfate can be in any ratio be used. Suitable organic peroxides are examples wise acetylacetone peroxide, methyl ethyl ketone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-amyl perpivalate, tert-Bu tylperpivalate, tert-butyl perneohexanoate, tert-butyl perisobuty rat, tert-butyl per-2-ethylhexanoate, tert-butyl perisononanoate, tert-butyl permaleate, tert-butyl perbenzoate, tert-butyl per-3,5,5-tri-methylhexanoate and tert-amyl perneodecanoate. Wei Other suitable polymerization initiators are azo starters, e.g. B. 2,2'-azobis- (2-amidinopropane) dihydrochloride, 2,2'-azobis- (N, N-di methylene) isobutyramidine dihydrochloride, 2- (carbamoylazo) iso butyronitrile and 4,4'-azobis (4-cyanovaleric acid). The called Polymerization initiators are used in conventional amounts sets, e.g. B. in amounts of 0.01 to 5, preferably 0.1 to 2 mol%, based on the monomers to be polymerized.
Die Redoxkatalysatoren enthalten als oxidierende Komponente min destens eine der oben angegebenen Perverbindungen und als redu zierende Komponente beispielsweise Ascorbinsäure, Glukose, Sor bose, Ammonium- oder Alkalimetall-hydrogensulfit, -sulfit, -thio sulfat, -hyposulfit, -pyrosulfit oder -sulfid, Metallsalze, wie Eisen-II-ionen oder Silberionen oder Natriumhydroxymethylsulfoxy lat. Vorzugsweise verwendet man als reduzierende Komponente des Redoxkatalysators Ascorbinsäure oder Natriumpyrosulfit. Bezogen auf die bei der Polymerisation eingesetzte Menge an Monomeren verwendet man 1.10-5 bis 1 Mol.-% der reduzierenden Komponente des Redoxkatalysatorsystems und 1.10-5 bis 5 Mol.-% der oxidierenden Komponente des Redoxkatalysators. Anstelle der oxidierenden Kom ponente des Redoxkatalysators oder zusätzlich kann man auch einen oder mehrere wasserlösliche Azostarter verwenden.The redox catalysts contain at least one of the above per-compounds as the oxidizing component and as reducing component, for example ascorbic acid, glucose, sorbose, ammonium or alkali metal hydrogen sulfite, sulfite, thiosulfate, hyposulfite, pyrosulfite or sulfide, metal salts , such as iron (II) ions or silver ions or sodium hydroxymethylsulfoxy lat. Ascorbic acid or sodium pyrosulfite is preferably used as the reducing component of the redox catalyst. Based on the amount of monomers used in the polymerization, 1.10 -5 to 1 mol% of the reducing component of the redox catalyst system and 1.10 -5 to 5 mol% of the oxidizing component of the redox catalyst are used. Instead of the oxidizing component of the redox catalyst or in addition, one or more water-soluble azo starters can also be used.
Bevorzugt wird im erfindungsgemäßen Verfahren ein Redoxsystem be stehend aus Wasserstoffperoxid, Natriumperoxodisulfat und Ascor binsäure eingesetzt. In einer üblichen Ausführungsform werden diese Komponenten in den Konzentrationen 1.10-2 Mol.-% Wasser stoffperoxid, 0,084 Mol.-% Natriumperoxodisulfat und 2,5.10-3 Mol.-% Ascorbinsäure bezogen auf die Monomere eingesetzt.A redox system consisting of hydrogen peroxide, sodium peroxodisulfate and ascorbic acid is preferably used in the process according to the invention. In a conventional embodiment, these components are used in concentrations of 1.10 -2 mol% of hydrogen peroxide, 0.084 mol% of sodium peroxodisulfate and 2.5.10 -3 mol% of ascorbic acid, based on the monomers.
Die wäßrige Monomerlösung kann den Initiator gelöst oder disper giert enthalten. Die Initiatoren können jedoch auch getrennt von der Monomerlösung dem Mischkneter zugeführt werden. The aqueous monomer solution can dissolve or disperse the initiator greed included. However, the initiators can also be separated from the monomer solution are fed to the mixer kneader.
Die Monomerlösung wird vor der Polymerisation von Restsauerstoff befreit. Dies geschieht mittels Inertgas, welches im Gleichstrom, Gegenstrom oder dazwischenliegenden Eintrittswinkeln eingeleitet werden kann. Eine gute Durchmischung kann beispielsweise mit Dü sen, statischen oder dynamischen Mischern oder Blasensäulen er zielt werden.The monomer solution is left over from the polymerization of residual oxygen exempted. This is done using inert gas, which is in cocurrent, Countercurrent or intermediate entry angles initiated can be. Good mixing can be done, for example, with Dü static or dynamic mixers or bubble columns aims to be.
Die Monomerlösung wird ebenfalls mit einem Inertgasstrom durch den Reaktor geführt. Bevorzugt beträgt der Massendurchsatz an Monomerlösung mindestens 1000, besonders bevorzugt mindestens 2000 und insbesondere mindestens 3000 kg/hm3 (Reaktorvolumen) und der Inertgasstrom mindestens 100 l/hm3 (Reaktorvolumen).The monomer solution is also passed through the reactor with an inert gas stream. The mass throughput of monomer solution is preferably at least 1000, particularly preferably at least 2000 and in particular at least 3000 kg / hm 3 (reactor volume) and the inert gas stream is at least 100 l / hm 3 (reactor volume).
Als Inertgase können unabhängig voneinander Stickstoff, ein Edel gas wie Argon, Kohlenmonoxid, Kohlendioxid, Schwefelhexafluorid oder Mischungen dieser Gase verwendet werden. Dabei ist es möglich das Inertgas ganz oder teilweise durch eine chemische Reaktion im Mischkneter zu erzeugen. Bevorzugt wird Stickstoff als Inertgas eingesetzt.Nitrogen, a noble, can be used independently of one another as inert gases gas such as argon, carbon monoxide, carbon dioxide, sulfur hexafluoride or mixtures of these gases can be used. It is the inert gas can be wholly or partly by a chemical To produce reaction in the mixer kneader. Nitrogen is preferred used as inert gas.
Das Reaktorvolumen kann je nach gewünschtem Umsatz variieren. Vorzugsweise beträgt das Reaktorvolumen mindestens 0,1 m3 beson ders bevorzugt 0,2 bis 20 m3 und insbesondere 0,2 bis 12 m3.The reactor volume can vary depending on the desired conversion. The reactor volume is preferably at least 0.1 m 3, particularly preferably 0.2 to 20 m 3 and in particular 0.2 to 12 m 3 .
Während an der Zugabestelle der Monomeren in den Mischer die Stoffe in flüssiger Form vorliegen geht die Konsistenz der Reak tionsmischung über einen hochviskosen Zustand in ein krümeliges Gel über, das durch die kontinuierliche Förderwirkung des Mischers am Ende des Mischers ausgetragen wird. Bei der Polymeri sation entsteht ein Gel, das im Mischer zu einem feinteiligen krümeligen Gel zerteilt und als solches dann ausgetragen wird. Wichtig ist dabei, daß während der Polymerisation im Mischer ein Teil des Wasser entfernt wird, so daß am Ende des Mischers krüme lige Gelteilchen mit einem Feststoffgehalt von 20 bis 100 Gew.-% anfallen.While at the addition point of the monomers in the mixer the Substances in liquid form are the consistency of the reak tion mixture over a highly viscous state into a crumbly one Gel over that through the continuous promotional effect of the Mixer is discharged at the end of the mixer. At the Polymeri a gel is formed which becomes a fine particle in the mixer crumbled gel and then discharged as such. It is important that during the polymerization in the mixer Part of the water is removed so that at the end of the mixer bends lige gel particles with a solids content of 20 to 100 wt .-% attack.
Im erfindungsgemäßen Verfahren einsetzbare Mischkneter sind von der Firma List erhältlich und beispielsweise in der CH-A-664 704, EP-A-517 068, WO 97/12666, DE-A-21 23 956, EP-A-603 525, DE-A-195 36 944 und DE-A-41 18 884 beschrieben.Mixing kneaders which can be used in the process according to the invention are from available from List and for example in CH-A-664 704, EP-A-517 068, WO 97/12666, DE-A-21 23 956, EP-A-603 525, DE-A-195 36 944 and DE-A-41 18 884.
Solche Kneter mit 2 Wellen erzielen durch die Anordnung der Knet- und Transportelemente eine hohe Selbstreinigung, die für eine kontinuierliche Polymerisation eine wichtige Anforderung ist. Vorzugsweise rotieren die beiden Wellen gegenläufig zueinander. Such kneaders with 2 shafts achieve by the arrangement of the kneading and transport elements a high level of self-cleaning, which is essential for a continuous polymerization is an important requirement. The two shafts preferably rotate in opposite directions to one another.
Auf der Rührwelle sind die Scheibensegmente propellerartig an geordnet. Als Knet- und Transportelemente sind z. B. wandgängige Mischbarren sowie L- oder U-förmig ausgeformte Aufsätze geeignet.The disk segments on the agitator shaft are propeller-like orderly. As kneading and transport elements such. B. wall-mounted Mixed bars as well as L- or U-shaped attachments are suitable.
Der Mischkneter kann nach Bedarf beheizt oder gekühlt werden. Die Monomerlösung wird darin bei einer Temperatur in dem Bereich von 0 bis 140°C und unter Normaldruck polymerisiert. Bevorzugt beträgt die Temperatur 20 bis 120°C und insbesondere 40 bis 120°C. Die maximale Temperatur beträgt bei einer bevorzugten Verfahrens variante mindestens 70°C, besonders bevorzugt mindestens 80°C und insbesondere mindestens 90°C, die Abgastemperatur mindestens 60°C, besonders bevorzugt mindestens 80°C und insbesondere mindestens 90°C und die Produkttemperatur beim Austrag aus dem Reaktor min destens 60°C, besonders bevorzugt mindestens 75°C und insbesondere mindestens 85°C.The mixer kneader can be heated or cooled as required. The Monomer solution is therein at a temperature in the range of 0 to 140 ° C and polymerized under normal pressure. Is preferably the temperature 20 to 120 ° C and in particular 40 to 120 ° C. The maximum temperature is in a preferred method variant at least 70 ° C, particularly preferably at least 80 ° C and in particular at least 90 ° C, the exhaust gas temperature at least 60 ° C, particularly preferably at least 80 ° C. and in particular at least 90 ° C and the product temperature when discharging from the reactor min at least 60 ° C, particularly preferably at least 75 ° C and in particular at least 85 ° C.
Bevorzugt wird das erfindungsgemäße Verfahren so durchgeführt, daß der Anteil der Wärmeabfuhr durch Verdampfung von Wasser aus dem Reaktionsgemisch mindestens 15% und besonders bevorzugt min destens 25% der Reaktionswärme beträgt.The method according to the invention is preferably carried out in such a way that that the share of heat dissipation from water evaporation the reaction mixture at least 15% and particularly preferably min is at least 25% of the heat of reaction.
Ferner werden Verfahrensvarianten bevorzugt bei denen der Anteil der Wärmeabfuhr durch den Produktaustrag mindestens 45% und ins besondere mindestens 55% der Reaktionswärme beträgt.Process variants are also preferred in which the proportion heat dissipation through the product discharge at least 45% and ins especially at least 55% of the heat of reaction.
Bevorzugt werden Verfahren, bei denen die Reaktionswärme zu ins gesamt mindestens 50%, besonders bevorzugt zu mindestens 70% und insbesondere zu mindestens 90% durch Produktaustrag und Wasserverdampfung abgeführt wird.Methods are preferred in which the heat of reaction is ins total at least 50%, particularly preferably at least 70% and in particular at least 90% through product discharge and Evaporation of water is carried away.
Nach einer ganz besonders bevorzugten Verfahrensvariante findet keine Wärmeabfuhr über die Kühlung der Reaktorwände statt.According to a very particularly preferred process variant no heat dissipation takes place via the cooling of the reactor walls.
Das bei der Polymerisation anfallende Gel hat einen Wassergehalt von 0 bis 80 Gew.-%, bevorzugt von 40 bis 70 Gew.-%. Dieser rela tiv geringe Feuchtigkeitsgehalt bei bereits rieselfähigem Gel, das nicht verklumpt, senkt die anschließend zur Trocknung aufzu bringende Energie.The gel obtained during the polymerization has a water content from 0 to 80% by weight, preferably from 40 to 70% by weight. This rela tiv low moisture content of free-flowing gel, that does not clump together, then lowers it for drying bringing energy.
Das Herstellverfahren zeichnet sich durch geringe Verweilzeiten im Reaktor und damit eine gute Raum/Zeit Ausbeute aus. So werden selbst bei Verweilzeiten unter 30 Minuten bei einem Reaktor volumen von 300 l feinteilige gelförmige Polymerisate mit einem sehr geringen Restmonomergehalt gefunden. Dies erspart die sonst aufwendigen Abtrennverfahren und erhöht die Ausbeute. Besonders bevorzugt werden Verfahrensvarianten mit einem hohen Massendurch satz, der Verweilzeiten unter 20 Minuten und sogar unter 10 Minu ten ermöglicht.The manufacturing process is characterized by short residence times in the reactor and thus a good space / time yield. So be even with residence times of less than 30 minutes in a reactor volume of 300 l of finely divided gel-like polymers with a very low residual monomer content found. This saves them otherwise elaborate separation process and increases the yield. Especially process variants with a high mass diameter are preferred set, the dwell times under 20 minutes and even under 10 minutes enables.
Das den Reaktor verlassende Polymergel wird im Anschluß in einem Verweilbehälter bei Temperaturen von 50 bis 120°C vorzugsweise 80 bis 100°C gelagert. Die Verweilzeit beträgt in der Regel 0 bis 3 Stunden, vorzugsweise 5 bis 30 Minuten. Der Behälter kann ein nach oben offener Behälter sein, möglich ist jedoch auch ein ver schlossener Behälter, an den ein leichtes Vakuum angelegt wird.The polymer gel leaving the reactor is then in a Retention tanks at temperatures from 50 to 120 ° C, preferably 80 stored up to 100 ° C. The dwell time is usually 0 to 3 Hours, preferably 5 to 30 minutes. The container can be a be open container upwards, but a ver is also possible closed container to which a slight vacuum is applied.
Der Trocknungsschritt kann nach allen bekannten Verfahrensweisen erfolgen, z. B. in einer Wirbelschicht, auf einem Umlufttrock nungsband, Vakuumtrocknungsband oder mit Hilfe einer Mikrowellen trocknung, oder bevorzugt unter vermindertem Druck in einem ein welligen Kneter unter intensivem Durchkneten des Polymergels. Dieser Trocknungsschritt wird vorzugsweise in einem ein- oder mehrwelligen Kneter bei einem Druck von 5 bis 300, vorzugsweise 20 bis 70 mbar und Temperaturen von 30 bis 170°C durchgeführt. Nach dem Trocknen erhält man ein rieselfähiges Polymergel, das eine sehr hohe Wasseraufnahme hat und als Bodenverbesserungs mittel bzw. als Absorptionsmittel in Hygieneartikeln, z. B. Win deln Verwendung finden kann. Die in den Beispielen angegebenen Teile sind Gewichtsteile, die Angaben in Prozent beziehen sich auf das Gewicht der Stoffe.The drying step can be carried out according to all known procedures take place, e.g. B. in a fluidized bed, on a circulating air dryer belt, vacuum drying belt or using a microwave drying, or preferably under reduced pressure in one wavy kneader with intensive kneading of the polymer gel. This drying step is preferably carried out in one or multi-shaft kneader at a pressure of 5 to 300, preferably 20 to 70 mbar and temperatures of 30 to 170 ° C carried out. After drying, a free-flowing polymer gel is obtained has a very high water absorption and as a soil improvement medium or as an absorbent in hygiene articles, e.g. B. Win can be used. The given in the examples Parts are parts by weight, the percentages are based on on the weight of the fabrics.
Zu Bestimmung der CRC wurden 0,2 g hydrogel-formendes Polymer (Kornfraktion 106-850 µm) in einem 60 × 85 mm großen Teebeutel eingewogen, der anschließend verschweißt wurde. Der Teebeutel wurde dann in einen Überschuß von 0,9 gew.-%iger Kochsalzlösung gegeben (mindestens 0,83 l Kochsalz Lösung/1 g hydrogel-formen des Polymer). Nach 30 Minuten Quellzeit wurde der Teebeutel aus der Kochsalz-Lösung genommen und bei 250 G drei Minuten zentrifu giert. Durch Wägung des zentrifugierten Teebeutels wurde die von dem hydrogel-formenden Polymer festgehaltene Flüssigkeitsmenge ermittelt.To determine the CRC, 0.2 g of hydrogel-forming polymer was used (Grain fraction 106-850 µm) in a 60 × 85 mm tea bag weighed, which was then welded. The tea bag was then poured into an excess of 0.9% saline given (at least 0.83 l saline solution / 1 g hydrogel forms of the polymer). After 30 minutes of swelling, the tea bag became out the saline solution taken and centrifuged at 250 G for three minutes yaws. By weighing the centrifuged tea bag, the by amount of liquid retained in the hydrogel-forming polymer determined.
Absorption unter Gewichtsbelastung AUL 0,7 psi (4826,5 Pa).Absorption under weight AUL 0.7 psi (4826.5 Pa).
Die Meßzelle zur Bestimmung der AUL 0,7 psi (4826,5 Pa) ist ein
Plexiglas-Zylinder mit einem Innendurchmesser von 60 mm und einer
Höhe von 50 mm, der an der Unterseite einen angeklebten Edel
stahl-Siebboden mit einer Maschenweite von 36 µm besitzt. Zu der
Meßzelle gehört weiterhin eine Plastikplatte mit einem Durch
messer von 59 mm und ein Gewicht, welches zusammen mit der
Plastikplatte in die Meßzelle hineingestellt werden kann. Das
Gewicht der Plastikplatte und des Gewichts beträgt zusammen 1345 g.
Zur Durchführung der Bestimmung der AUL 0,7 psi (4826,5 Pa)
wird das Gewicht des leeren Plexiglas-Zylinders und der Plastik
platte gemessen und als Wo notiert. Dann werden 0,900 ± 0,005 g
hydrogel-formendes Polymer (Korngrößenverteilung: 150-800 µm) in
den Plexiglas-Zylinder eingewogen und möglichst gleichmäßig auf
dem Edelstahl-Siebboden verteilt. Anschließend wird die Plexi
glasplatte vorsichtig in den Plexiglaszylinder hineingelegt, die
gesamte Einheit gewogen und das Gewicht als Wa notiert. Nun wird
das Gewicht auf die Plastikplatte in dem Plexiglas-Zylinder
gestellt. In die Mitte einer Petrischale mit einem Durchmesser
von 200 mm und einer Höhe von 30 mm wird eine keramische Filter
platte mit einem Durchmesser von 120 mm und der Porosität 0
gelegt und soviel 0,9 gew.-%ige Natriumchlorid-Lösung eingefüllt,
daß die Flüssigkeitsoberfläche mit der Filterplattenoberfläche
abschließt, ohne das die Oberfläche der Filterplatte bedeckt
wird. Anschließend wird ein rundes Filterpapier mit einem Durch
messer von 90 mm und einer Porengröße < 20 µm (Schwarzband 589 von
Schleicher & Schüll) auf die keramische Filterplatte gelegt. Der
hydrogel-formendes Polymer enthaltende Plexiglaszylinder wird mit
Plastikplatte und Gewicht nun auf das Filterpapier gestellt und
dort für 60 Minuten belassen. Nach dieser Zeit wird die komplette
Einheit aus der Petrischale vom Filterpapier herausgenommen und
anschließend das Gewicht aus dem Plexiglaszylinder entfernt. Der
gequollenes Hydrogel enthaltende Plexiglaszylinder wird zusammen
mit der Plastikplatte ausgewogen und das Gewicht als Wb notiert.
Die AUL 0,7 psi (4826,5 Pa) berechnet sich gemäß:
The measuring cell for determining the AUL 0.7 psi (4826.5 Pa) is a plexiglass cylinder with an inner diameter of 60 mm and a height of 50 mm, which has a glued-on stainless steel sieve bottom with a mesh size of 36 µm on the underside owns. To the measuring cell also includes a plastic plate with a diameter of 59 mm and a weight that can be placed together with the plastic plate in the measuring cell. The weight of the plastic plate and the weight together is 1345 g. To carry out the determination of the AUL 0.7 psi (4826.5 Pa), the weight of the empty Plexiglas cylinder and the plastic plate is measured and noted as W o . Then 0.900 ± 0.005 g of hydrogel-forming polymer (particle size distribution: 150-800 µm) is weighed into the plexiglass cylinder and distributed as evenly as possible on the stainless steel sieve plate. Then the plexiglass plate is carefully placed in the plexiglass cylinder, the entire unit weighed and the weight noted as W a . Now the weight is placed on the plastic plate in the plexiglass cylinder. In the middle of a petri dish with a diameter of 200 mm and a height of 30 mm, a ceramic filter plate with a diameter of 120 mm and the porosity 0 is placed and 0.9% by weight sodium chloride solution is filled in so that the Liquid surface is flush with the filter plate surface without covering the surface of the filter plate. Then a round filter paper with a diameter of 90 mm and a pore size <20 µm (black tape 589 from Schleicher & Schüll) is placed on the ceramic filter plate. The plexiglass cylinder containing the hydrogel-forming polymer is now placed with the plastic plate and weight on the filter paper and left there for 60 minutes. After this time, the complete unit is removed from the Petri dish from the filter paper and then the weight is removed from the Plexiglas cylinder. The plexiglass cylinder containing swollen hydrogel is weighed out together with the plastic plate and the weight is noted as W b . The AUL 0.7 psi (4826.5 Pa) is calculated according to:
AUL 0,7 psi = [Wb - Wa]/[Wa - Wo].AUL 0.7 psi = [W b - W a ] / [W a - W o ].
Die nachfolgenden Beispiele sollen die Erfindung näher erläutern.The following examples are intended to explain the invention in more detail.
40 Gew.-% Monomer, vor der Polymerisation bestehend aus Acryl
säure und Natriumacrylat mit einem Neutralisationsgrad der Acryl
säure von 77 mol-%. Es wurde Acrylsäure neutralisiert (Spezifika
tion: mind. 99,5 Gew.-% Acrylsäure, max. 0,1 Gew.-% Wasser,
max. 500 ppm Diacrylsäure, 180-200 ppm Monomethylhydrochinon
ether, < 2000 ppm Essigsäure, < 600 ppm Propionsäure). Nach der
Neutralisation wurde die Mischung maximal 6 Stunden gelagert ehe
sie zur Polymerisation eingesetzt wurde. Zur Initiierung der
radikalischen Polymerisation wurde folgendes System verwendet:
0,005 Gew.-% Wasserstoffperoxid und 0,006 Gew.-% Ascorbinsäure
und 0,28 Gew.-% Natriumperoxodisulfat, wobei alle Mengenangaben
auf die in der Reaktionslösung vorhandenen Monomere - ausgedrückt
als Acrylsäure - bezogen sind. Als mehrfach ethylenisch unge
sättigter Vernetzer wurde Polyethylenglykol-400-diacrylat (Cray
Valley) in einer Einsatzmenge von 0,45 Gew.-% bezogen auf die in
der Reaktionslösung vorhandenen Monomere - ausgedrückt als Acryl
säure - verwendet. Der Vernetzer wurde zusammen mit der wäßrigen
Monomerlösung gemischt und diese Lösung durch Einleiten von
Stickstoff inertisiert.40 wt .-% monomer, before the polymerization consisting of acrylic acid and sodium acrylate with a degree of neutralization of acrylic acid of 77 mol%. Acrylic acid was neutralized (specification: at least 99.5% by weight acrylic acid, max.0.1% by weight water, max. 500 ppm diacrylic acid, 180-200 ppm monomethylhydroquinone ether, <2000 ppm acetic acid, <600 ppm propionic acid). After neutralization, the mixture was stored for a maximum of 6 hours before it was used for the polymerization. The following system was used to initiate the radical polymerization:
0.005% by weight of hydrogen peroxide and 0.006% by weight of ascorbic acid and 0.28% by weight of sodium peroxodisulfate, all the amounts given being based on the monomers present in the reaction solution, expressed as acrylic acid. Polyethylene glycol 400 diacrylate (Cray Valley) was used as a polyethylenically unsaturated crosslinker in an amount of 0.45% by weight, based on the monomers present in the reaction solution, expressed as acrylic acid. The crosslinker was mixed together with the aqueous monomer solution and this solution was rendered inert by introducing nitrogen.
Die einzelnen Komponenten dieser Reaktionslösung (verdünnte wäßrige Lösungen von Wasserstoffperoxid, Ascorbinsäure, Natrium peroxodisulfat und die Monomer/Vernetzerlösung) wurden getrennt in den Knetreaktor eindosiert und dort während des Einlaufens im Reaktor gemischt, wobei die Polymerisation schon während des Mischens zügig startete.The individual components of this reaction solution (diluted aqueous solutions of hydrogen peroxide, ascorbic acid, sodium peroxodisulfate and the monomer / crosslinker solution) were separated metered into the kneading reactor and there in the Reactor mixed, the polymerization during the Mixing started quickly.
Es wurden 600 kg/h Reaktionslösung in einen List ORP 250 Conti kneter (Fa. List, Arisdorf, Schweiz) eingebracht und das im Kneter durch Polymerisation erzeugte Gel wurde kontinuierlich ausgetragen. Die Temperatur des Kühlwassers im Mantel betrug 40°C bei einem gesamten Kühlwasserdurchsatz durch den Mantel von 12 m3/h. Während der Polymerisation wurden 14 m3/h Stickstoff als Inertgas durch diesen Kneter geführt. Das Reaktionsvolumen betrug 300 l.600 kg / h of reaction solution were introduced into a List ORP 250 Conti kneader (from List, Arisdorf, Switzerland) and the gel produced in the kneader by polymerization was continuously discharged. The temperature of the cooling water in the jacket was 40 ° C. with a total cooling water throughput of 12 m 3 / h through the jacket. During the polymerization, 14 m 3 / h of nitrogen were passed through this kneader as an inert gas. The reaction volume was 300 l.
Der Reaktor wurde so betrieben, daß 62% der Reaktionswärme über die Reaktorwand durch die Mantelkühlung abgeführt wurde und 38% der Reaktionswärme durch das warme Produktgel ausgetragen wurde. Unter diesen Bedingungen fand kein Wärmeaustrag durch Wasserver dampfung statt.The reactor was operated so that 62% of the heat of reaction the reactor wall was removed through the jacket cooling and 38% the heat of reaction was discharged through the warm product gel. Under these conditions, there was no heat dissipation from water steaming instead.
Die Reaktionslösung hatte am Zulauf eine Temperatur von 23,5°C, und das Produktgel besaß am Austrag eine Temperatur von 64,5°C. Es wurden maximale Produkttemperaturen < 80°C im Reaktor gemessen. Die Verweilzeit des Produkts im Reaktor betrug unter 15 min.The reaction solution had a temperature of 23.5 ° C. at the inlet, and the product gel had a temperature of 64.5 ° C at the discharge. It maximum product temperatures <80 ° C were measured in the reactor. The residence time of the product in the reactor was less than 15 minutes.
Im erhaltenen Produktgel wurde analytisch ein Restacrylsäurege halt von 1,23 Gew.-% und ein Feststoffgehalt von 41,0 Gew.-% gefunden. Das Gel wurde getrocknet, gemahlen und durch sieben eine Korngrößenfraktion von 100-800 µm erhalten. Das getrocknete Polymer besaß eine Zentrifugenretentionskapazität von 38,8 g/g. Der pH-Wert des Polymers betrug 6,1. A residual acrylic acid was analytically obtained in the product gel obtained content of 1.23% by weight and a solids content of 41.0% by weight found. The gel was dried, ground and sifted through receive a grain size fraction of 100-800 microns. The dried one Polymer had a centrifuge retention capacity of 38.8 g / g. The pH of the polymer was 6.1.
Anschließend wurden 20 g Polymer (Korngrößenfraktion 100-800 µm)
in einem Labormischer (Waring-Mischer) mit Mischaufsatz und abge
stumpften Mischblättern vorgelegt. Bei eingeschaltetem Mischer
und niedriger Umdrehungszahl wurden 1 g Nachvernetzungslösung
enthaltend 12 mg Ethylenglykoldiglycidylether gelöst in einer
Mischung aus 33 Gew.-% 1,2-Propylenglykol und 67 Gew.-% Wasser
zudosiert. Das feuchte Polymerpulver wurde danach dem Mischer
entnommen und in einer Petrischale bei 150°C 60 Minuten lang im
Umluftschrank getrocknet. Nach Absieben der Grobfraktion (< 800
Mikrometer) wurde das erhaltene Produkt anwendungstechnisch
untersucht:
Zentrifugenretentionskapazität, CRC = 32,2 g/g
AUL 0,7 psi: 26,0 g/g.Subsequently, 20 g of polymer (particle size fraction 100-800 microns) were placed in a laboratory mixer (Waring mixer) with a mixing attachment and blunted mixing blades. When the mixer was switched on and the speed of rotation was low, 1 g of postcrosslinking solution containing 12 mg of ethylene glycol diglycidyl ether dissolved in a mixture of 33% by weight of 1,2-propylene glycol and 67% by weight of water was metered in. The moist polymer powder was then removed from the mixer and dried in a petri dish at 150 ° C. for 60 minutes in a circulating air cabinet. After the coarse fraction had been sieved off (<800 micrometers), the product obtained was examined in terms of application technology:
Centrifuge retention capacity, CRC = 32.2 g / g
AUL 0.7 psi: 26.0 g / g.
Wie in Beispiel 1 beschrieben, wurden 600 kg/h Reaktionslösung kontinuierlich polymerisiert, jedoch wurde die Temperatur des Kühlwassers im Reaktormantel auf 90°C geregelt und der Kühlmittel durchfluß wurde auf ca. 6 m3/h gedrosselt. Der Reaktor wurde so betrieben, daß 64% der Reaktionswärme über den Produktaustrag und 36% über die Verdampfung des Reaktionswassers abgeführt wur den. Es wurden Reaktionstemperaturen von 96-98°C im Reaktor festgestellt. Die Verweilzeit im Reaktor betrug unter 15 Minuten. Es fand keine Wärmeabfuhr über die Reaktorwand statt. Es wurde ein Restmonomerengehalt an Acrylsäure im Produktgel von 0,25 Gew.-% ermittelt bei einem Feststoffgehalt von 43,0 Gew.-%. Die Reaktoreintrittstemperatur der Reaktionslösung betrug 23,2°C, und die Reaktoraustrittstemperatur des erhaltenen Produktgels be trug 93,2°C.As described in Example 1, 600 kg / h of reaction solution were polymerized continuously, but the temperature of the cooling water in the reactor jacket was regulated at 90 ° C. and the coolant flow was throttled to about 6 m 3 / h. The reactor was operated such that 64% of the heat of reaction was removed via the product discharge and 36% via the evaporation of the water of reaction. Reaction temperatures of 96-98 ° C were found in the reactor. The residence time in the reactor was less than 15 minutes. There was no heat dissipation via the reactor wall. A residual monomer content of acrylic acid in the product gel of 0.25% by weight was determined with a solids content of 43.0% by weight. The reactor inlet temperature of the reaction solution was 23.2 ° C, and the reactor outlet temperature of the product gel obtained was 93.2 ° C.
Das erhaltene Gel wurde analog Bsp. 1 getrocknet, gemahlen, gesiebt und oberflächennachvernetzt. Die anwendungstechnischen Ergebnisse sind Tabelle 1 zu entnehmen. Das getrocknete Polymer hatte vor der Oberflächennachvernetzung eine Zentrifugenretenti onskapazität von 37,8 g/g und einen pH-Wert von 6,1.The gel obtained was dried analogously to Example 1, ground, sieved and post-crosslinked. The application technology Results are shown in Table 1. The dried polymer had a centrifuge retenti before surface post-crosslinking on capacity of 37.8 g / g and a pH of 6.1.
Es wurde ein Versuch analog zu Beispiel 2 durchgeführt, jedoch wurden statt 600 kg/h nur 450 kg/h an Reaktionslösung dem Reaktor zugeführt. Die Verweilzeit im Reaktor betrug nun ca. 20 min. An experiment was carried out analogously to Example 2, however instead of 600 kg / h, only 450 kg / h of reaction solution were added to the reactor fed. The residence time in the reactor was now about 20 minutes.
Es wurde ein Restmonomerengehalt im Produktgel von 0,15 Gew.-% ermittelt bei einem Feststoffgehalt von 43,1 Gew.-%. Die Reaktor eintrittstemperatur der Reaktionslösung betrug 23,4°C, und die Re aktoraustrittstemperatur des erhaltenen Produktgels betrug 91,7°C. Es wurden maximale Reaktionstemperaturen von 95-97°C im Reaktor gemessen.A residual monomer content of 0.15% by weight was found in the product gel. determined at a solids content of 43.1% by weight. The reactor inlet temperature of the reaction solution was 23.4 ° C, and the Re Actuator outlet temperature of the product gel obtained was 91.7 ° C. There were maximum reaction temperatures of 95-97 ° C in the reactor measured.
Das erhaltene Gel wurde analog Bsp. 1 getrocknet, gemahlen, ge siebt und oberflächennachvernetzt. Die anwendungstechnischen Ergebnisse sind in Tabelle 2 aufgeführt. Das getrocknete Polymer besaß vor der Oberflächennachvernetzung eine Zentrifugenreten tionskapazität von 39,5 g/g und einen pH-Wert von 6,1.The gel obtained was dried analogously to Example 1, ground, ge sieves and post-crosslinked. The application technology Results are shown in Table 2. The dried polymer had a centrifuge pedal before the surface post-crosslinking tion capacity of 39.5 g / g and a pH of 6.1.
Es wurde ein Versuch analog zu Beispiel 2 durchgeführt.An experiment was carried out analogously to Example 2.
Es wurde gefunden, daß der Restmonomerengehalt des Produktgels 0,30 Gew.-% betrug, während der Feststoffgehalt 42,9 Gew.-% be trug. Die Reaktoreintrittstemperatur der Reaktionslösung betrug 23,4°C, und die Reaktoraustrittstemperatur des erhaltenen Produkt gels betrug 93,2°C.It was found that the residual monomer content of the product gel Was 0.30% by weight, while the solids content was 42.9% by weight wore. The reactor inlet temperature of the reaction solution was 23.4 ° C, and the reactor outlet temperature of the product obtained gel was 93.2 ° C.
Das erhaltene Gel wurde analog Bsp. 1 getrocknet, gemahlen, gesiebt und oberflächennachvernetzt. Die anwendungstechnischen Ergebnisse sind in Tab. 2 aufgeführt. Das getrocknete Polymer besaß vor der Oberflächennachvernetzung eine Zentrifugenretenti onskapazität von 39,4 g/g und einen pH-Wert von 6,1.The gel obtained was dried analogously to Example 1, ground, sieved and post-crosslinked. The application technology Results are shown in Tab. 2. The dried polymer had a centrifuge retenti before surface post-crosslinking on capacity of 39.4 g / g and a pH of 6.1.
Es wurde ein Versuch analog zu Beispiel 2 durchgeführt, jedoch wurden diesmal 750 kg/h Reaktionslösung dem Reaktor zugeführt. Die Verweilzeit im Reaktor betrug jetzt nur noch ca. 12 min.An experiment was carried out analogously to Example 2, however This time 750 kg / h of reaction solution were fed to the reactor. The residence time in the reactor was now only about 12 minutes.
Es wurde ein Restmonomergehalt des Produktgels von 0,25 Gew.-% und ein Feststoffgehalt von 43,0 Gew.-% ermittelt. Die Reaktor eintrittstemperatur der Reaktionslösung betrug 23,4°C, und die Re aktoraustrittstemperatur des erhaltenen Produktgels betrug 94,8°C. Es wurden maximale Produkttemperaturen von 97-99°C im Reaktor gemessen.A residual monomer content of the product gel of 0.25% by weight and a solids content of 43.0% by weight was determined. The reactor inlet temperature of the reaction solution was 23.4 ° C, and the Re Actuator outlet temperature of the product gel obtained was 94.8 ° C. There were maximum product temperatures of 97-99 ° C in the reactor measured.
Das erhaltene Gel wurde analog Bsp. 1 getrocknet, gemahlen, ge siebt und oberflächennachvernetzt. Die anwendungstechnischen Ergebnisse sind in Tabelle 2 aufgeführt. Das getrocknete Polymer besaß vor der Nachvernetzung eine Zentrifugenretentionskapazität von 36,9 g/g und einen pH-Wert von 6,1.The gel obtained was dried analogously to Example 1, ground, ge sieves and post-crosslinked. The application technology Results are shown in Table 2. The dried polymer had a centrifuge retention capacity before post-crosslinking of 36.9 g / g and a pH of 6.1.
Als gesamte "Reaktionswärme" wird die Summe der eigentlichen Po lymerisationswärme und des Wärmeeintrags ins Produkt durch mecha nische Rührung angenommen.The total "heat of reaction" is the sum of the actual Po heat of polymerization and the heat input into the product by mecha African emotion accepted.
Die Kühlwassertemperatur betrug bei allen Versuchen 90°C - die Edukteintrittstemperatur lag bei 22-24°C.The cooling water temperature was 90 ° C in all tests The starting material temperature was 22-24 ° C.
Als gesamte "Reaktionswärme" wird die Summe der eigentlichen Polymerisationswärme und des Wärmeeintrags ins Produkt durch mechanische Rührung angenommen.As the total "heat of reaction", the sum of the actual Polymerization heat and the heat input into the product mechanical agitation assumed.
Claims (9)
- a) wasserlöslichen, monoethylenisch ungesättigten Monomeren,
- b) 0,001 bis 5 Mol-% bezogen auf die Monomere (a), mindes tens zwei ethylenisch ungesättigte Doppelbindungen ent haltenden Monomeren und
- c) 0 bis 20 Mol-% bezogen auf die Monomere (a) wasserun löslichen monoethylenisch ungesättigten Monomeren
- a) water-soluble, monoethylenically unsaturated monomers,
- b) 0.001 to 5 mol% based on the monomers (a), at least two monomers containing ethylenically unsaturated double bonds and
- c) 0 to 20 mol% based on the monomers (a) water-insoluble monoethylenically unsaturated monomers
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DE19955861A DE19955861A1 (en) | 1999-11-20 | 1999-11-20 | Continuous production of crosslinked gel polymer for use e.g. as an absorber involves polymerisation of monomers in a multi-screw machine with heat removal by evaporation of water and product take-off |
DE50014971T DE50014971D1 (en) | 1999-11-20 | 2000-11-10 | Process for the continuous preparation of crosslinked finely divided gel-like polymers |
TR2004/00487T TR200400487T4 (en) | 1999-11-20 | 2000-11-10 | Continuous production method of cross-woven polymers. |
BRPI0015680-9A BR0015680B1 (en) | 1999-11-20 | 2000-11-10 | process for the continuous production of fine cross-linked particles of polymeric gel. |
AT03022084T ATE386057T1 (en) | 1999-11-20 | 2000-11-10 | METHOD FOR THE CONTINUOUS PRODUCTION OF CROSS-LINKED FINE PARTICLE GEL-SHAPED POLYMERS |
US10/111,428 US6710141B1 (en) | 1999-11-20 | 2000-11-10 | Method for continuously producing cross-linked fine-particle geleous polymerizates |
PCT/EP2000/011098 WO2001038402A1 (en) | 1999-11-20 | 2000-11-10 | Method for continuously producing cross-linked fine-particle geleous polymerizates |
CNB008158509A CN1142188C (en) | 1999-11-20 | 2000-11-10 | Method for continuously producing cross-linked fine-particle geleous polymerizates |
AT00974512T ATE260937T1 (en) | 1999-11-20 | 2000-11-10 | METHOD FOR THE CONTINUOUS PRODUCTION OF CROSS-LINKED FINE PARTICLE GEL-SHAPED POLYMERS |
CA002390871A CA2390871A1 (en) | 1999-11-20 | 2000-11-10 | Continuous production of crosslinked fine particles of polymer gel |
MXPA02004034A MXPA02004034A (en) | 1999-11-20 | 2000-11-10 | Method for continuously producing cross linked fine particle geleous polymerizates. |
JP2001540164A JP4511774B2 (en) | 1999-11-20 | 2000-11-10 | Continuous production method of cross-linked fine-grained gel-like polymer |
EP00974512A EP1237937B1 (en) | 1999-11-20 | 2000-11-10 | Method for continuously producing cross-linked fine-particle geleous polymerizates |
DE50005555T DE50005555D1 (en) | 1999-11-20 | 2000-11-10 | METHOD FOR THE CONTINUOUS PRODUCTION OF CROSS-LINKED FINE-PART GEL-SHAPED POLYMERS |
EP03022084A EP1384728B8 (en) | 1999-11-20 | 2000-11-10 | Method for continuously producing cross-linked fine-particle geleous polymerizates |
ES00974512T ES2216983T3 (en) | 1999-11-20 | 2000-11-10 | PROCEDURE FOR CONTINUOUS OBTAINING OF POLYMERS IN THE FORM OF A GEL FINALLY DIVIDED AND RETICULATED. |
US10/765,152 US20040186229A1 (en) | 1999-11-20 | 2004-01-28 | Continuous production of crosslinked fine particles of polymer gel |
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DE50005555T Expired - Lifetime DE50005555D1 (en) | 1999-11-20 | 2000-11-10 | METHOD FOR THE CONTINUOUS PRODUCTION OF CROSS-LINKED FINE-PART GEL-SHAPED POLYMERS |
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- 2000-11-10 CA CA002390871A patent/CA2390871A1/en not_active Abandoned
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- 2000-11-10 BR BRPI0015680-9A patent/BR0015680B1/en not_active IP Right Cessation
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- 2000-11-10 EP EP00974512A patent/EP1237937B1/en not_active Expired - Lifetime
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- 2000-11-10 JP JP2001540164A patent/JP4511774B2/en not_active Expired - Lifetime
- 2000-11-10 ES ES00974512T patent/ES2216983T3/en not_active Expired - Lifetime
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Also Published As
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MXPA02004034A (en) | 2002-10-11 |
EP1237937A1 (en) | 2002-09-11 |
DE50014971D1 (en) | 2008-03-27 |
EP1384728B1 (en) | 2008-02-13 |
TR200400487T4 (en) | 2004-04-21 |
US20040186229A1 (en) | 2004-09-23 |
ES2216983T3 (en) | 2004-11-01 |
CN1142188C (en) | 2004-03-17 |
US6710141B1 (en) | 2004-03-23 |
DE50005555D1 (en) | 2004-04-08 |
EP1384728A1 (en) | 2004-01-28 |
CA2390871A1 (en) | 2001-05-31 |
CN1391582A (en) | 2003-01-15 |
ATE386057T1 (en) | 2008-03-15 |
BR0015680B1 (en) | 2010-06-15 |
ATE260937T1 (en) | 2004-03-15 |
JP4511774B2 (en) | 2010-07-28 |
EP1237937B1 (en) | 2004-03-03 |
WO2001038402A1 (en) | 2001-05-31 |
BR0015680A (en) | 2002-08-06 |
EP1384728B8 (en) | 2008-04-02 |
JP2003514961A (en) | 2003-04-22 |
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